CN105086537B - A kind of transparent super-hydrophobic automatic cleaning coating - Google Patents
A kind of transparent super-hydrophobic automatic cleaning coating Download PDFInfo
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- CN105086537B CN105086537B CN201510506386.8A CN201510506386A CN105086537B CN 105086537 B CN105086537 B CN 105086537B CN 201510506386 A CN201510506386 A CN 201510506386A CN 105086537 B CN105086537 B CN 105086537B
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Abstract
A kind of transparent super-hydrophobic automatic cleaning coating, using the Nano particles of silicon dioxide of a step direct hydrolysis method anamorphic zone active hydrophobic group, then prepares coating, obtains the self-cleaning coating of high transparency.The self-cleaning coating is by with the hydrophobic Nano particles of silicon dioxide of active group, alcohols solvent and auxiliary agent composition.With the hydrophobic Nano particles of silicon dioxide content of active group 1% 10%, alcohols solvent content 90% 98%, auxiliary agent content 0.1% 1%.Light transmittance is more than 98% after coating film forming, and water contact angle is more than 150 °, with good self-cleaning performance, can be widely used for building glass curtain wall, vehicle glass, photovoltaic module, optics etc..
Description
Technical field
The present invention relates to a kind of transparent super-hydrophobic automatic cleaning coating, function of dominant technical field of polymer materials.
Background technology
Self-cleaning surface with " lotus leaf effect " has good super-hydrophobicity, stronger contamination resistance.Automatically cleaning is applied
Layer has the advantages such as water saving, energy-saving and environmental protection, increasingly gets more and more people's extensive concerning, and is the focus of current material subject research
One of.Current bionic super-hydrophobic coating is mainly by modifying low-surface energy substance in rough surface and improving low-surface energy substance
Roughness two ways is realized.
With going deep into for research, people progressively find transparency be super-hydrophobic coat build in highly important parameter it
One.Higher translucency causes bionic super-hydrophobic coating in automobile, aircraft and spacecraft windshield, skyscraper glass and outer
The fields such as wall, solar panel, optical instrument, which possess, is more widely applied prospect.But the transparency and roughness are two
The individual factor vied each other, controls suitable surface roughness, to reach that preferable surface transparency is grinding for the current field
Study carefully difficult point.Therefore, how to obtain the coating of optical clear and surface super hydrophobic turns into one of the technical bottleneck in the field.Mesh
The based superhydrophobic thin films surface transparency of preceding report is very poor, and the adhesion with base material is weaker, easily falls off so that its practical valency
Value is had a greatly reduced quality.
The preparation method of current bionical transparent hydrophobic coating mainly includes surface modification by low-surface energy substance, molten
Sol-gel, LBL self-assembly method, sedimentation, plasma technique etc., but there is preparation technology complexity, condition is harsh, if
The problems such as standby costliness production cost is high, is unfavorable for the actual use of bionical transparent hydrophobic coating.Analyzed based on more than, in coating
Seek a suitable equalization point between surface roughness and visible light transmissivity, and then realize the system of super-hydrophobicity and the transparency
One, by simple controllable process conditions, relatively low bionical transparent super thin of production cost is obtained using equipment simple to operate
Water paint turns into one of super-hydrophobic coat technology development priority direction.
The content of the invention
The purpose of the present invention is, the problem of being existed according to existing super-hydrophobic coating, proposes a kind of transparent hydrophobic from clear
Clean coating.
Realize that technical scheme is as follows：The present invention is using a step direct hydrolysis method anamorphic zone active hydrophobic group
Nano particles of silicon dioxide, then coating is prepared, obtain the self-cleaning coating of high transparency.
A kind of transparent super-hydrophobic automatic cleaning coating of the present invention is by with the hydrophobic Nano particles of silicon dioxide of active group, alcohols
The one-component curing system that solvent and auxiliary agent are mixed to form.
The Nano particles of silicon dioxide hydrophobic with active group is by tetraethyl orthosilicate, silane coupler, siliceous amine
Alkane is synthesized by direct hydrolysis；The Nano particles of silicon dioxide content hydrophobic with active group is total coating system mixing
The 1%-10% of thing weight.
The alcohols solvent be by ethanol and isopropanol, n-butanol, n-hexyl alcohol, the mixing of one or both of n-octyl alcohol and
Into mixed solvent；The alcohols solvent content is the 90%-98% of total coating system mixture weight.
The auxiliary agent includes one kind in butyl acrylate, allyl methacrylate, GMA
With 2- hydroxy-2-methyl -1- phenylacetones, benzophenone, one kind in salt compounded of iodine is mixed；The auxiliary agent content is total
The 0.1%-1% of coating system mixture weight.
The silane coupler is the siloxanes with active group, including one kind in KH570, KH560, KH561, is contained
Silicon amine alkane be can fast hydrolyzing produce ammonia catalysis tetraethyl orthosilicate generation Nano particles of silicon dioxide, while entering to nano-particle
One class compound of row hydrophobically modified, including HMDS, divinyl tetramethyl disilazane, the silicon amine of tetramethyl two
One kind in alkane.
The nano particle diameter is 10-200nm.
The active group is acrylate-based or epoxy radicals.
Light transmittance is more than 98% after the coating film forming, and water contact angle is more than 150 °, with good self-cleaning performance.
The beneficial effects of the invention are as follows, high transparency super-hydrophobic self-cleaning paint of the present invention be by with active group it is hydrophobic two
The one-component curing system that silicon oxide nanoparticle, alcohols solvent and auxiliary agent are mixed to form, with easy construction, material solidification
Quick the characteristics of.
The Nano particles of silicon dioxide hydrophobic with active group of the present invention is, by tetraethyl orthosilicate, silane coupler, to contain
Silicon amine alkane is synthesized by direct hydrolysis, simple with synthesis technique, and reaction condition is gentle, and reproducible, product structure is controllable
Feature.The high transparency super-hydrophobic self-cleaning paint of the present invention is formed by the component cross-link with curing activity, and material, which has, to be shunk
Rate is low, and adhesion strength is high, waterproof, corrosion resistant feature.
The high transparency super-hydrophobic self-cleaning paint of the present invention has very high transmitance in visible-range, does not influence glass
The optical property of glass.The high transparency super-hydrophobic self-cleaning paint of preparation has super-hydrophobicity, shows good self-cleaning performance,
Meet glass coating automatically cleaning application performance requirement.
High transparency super-hydrophobic self-cleaning paint of the present invention can be widely used for building glass curtain wall, vehicle glass, photovoltaic module,
Optics etc..
Brief description of the drawings
Fig. 1 is the light transmittance of film of the embodiment of the present invention；
Fig. 2 is the water contact angle image of film of the embodiment of the present invention.
Embodiment
Embodiment 1：Surface band methacrylic acid ester group hydrophobic silica nano-particle (MSiO2) 1 synthesis
2mL tetraethyl orthosilicates are taken, 0.12mL silane coupler KH570 add after adding 35mL absolute ethyl alcohols, stirring 15min
Enter 3mL HMDSs, continue to stir 0.5h, 3mL deionized waters are then slowly added dropwise, reaction 24h is stirred at room temperature, is formed
The alcohol dispersion liquid of Nano particles of silicon dioxide, the particle diameter of nano-particle is 40-80nm.
Embodiment 2：Surface band epoxy radicals hydrophobic silica nano-particle (ESiO2) 1 synthesis
2mL tetraethyl orthosilicates are taken, 0.12mL silane coupler KH560 add after adding 35mL absolute ethyl alcohols, stirring 15min
Enter 3mL HMDSs, continue to stir 0.5h, 3mL deionized waters are then slowly added dropwise, reaction 24h is stirred at room temperature, is formed
The alcohol dispersion liquid of Nano particles of silicon dioxide, the particle diameter of nano-particle is 30-70nm.
Embodiment 3：Surface band methacrylic acid ester group hydrophobic silica nano-particle (MSiO2) 2 synthesis
2mL tetraethyl orthosilicates are taken, 0.12mL silane coupler KH570 add after adding 35mL absolute ethyl alcohols, stirring 15min
Enter 3mL divinyl tetramethyl disilazanes, continue to stir 0.5h, 3mL deionized waters are then slowly added dropwise, reaction is stirred at room temperature
24h, forms the alcohol dispersion liquid of Nano particles of silicon dioxide, the particle diameter of nano-particle is 20-80 nm.
Embodiment 4：Surface band epoxy radicals hydrophobic silica nano-particle (ESiO2) 2 synthesis
2mL tetraethyl orthosilicates are taken, 0.12mL silane coupler KH560 add after adding 35mL absolute ethyl alcohols, stirring 15min
Enter 3mL divinyl tetramethyl disilazanes, continue to stir 0.5h, 3mL deionized waters are then slowly added dropwise, reaction is stirred at room temperature
24h, forms the alcohol dispersion liquid of Nano particles of silicon dioxide, the particle diameter of nano-particle is 20-70nm.
Embodiment 5：Surface band methacrylic acid ester group hydrophobic silica nano-particle (MSiO2) 3 synthesis
2mL tetraethyl orthosilicates are taken, 0.12mL silane coupler KH570 add after adding 35mL absolute ethyl alcohols, stirring 15min
Enter 3mL tetramethyl disilazanes, continue to stir 0.5h, 3mL deionized waters are then slowly added dropwise, reaction 24h is stirred at room temperature, is formed
The alcohol dispersion liquid of Nano particles of silicon dioxide, the particle diameter of nano-particle is 40-80nm.
Embodiment 6：Surface band epoxy radicals hydrophobic silica nano-particle (ESiO2) 3 synthesis
2mL tetraethyl orthosilicates are taken, 0.12mL silane coupler KH560 add after adding 35mL absolute ethyl alcohols, stirring 15min
Enter 3mL tetramethyl disilazanes, continue to stir 0.5h, 3mL deionized waters are then slowly added dropwise, reaction 24h is stirred at room temperature, is formed
The alcohol dispersion liquid of Nano particles of silicon dioxide, the particle diameter of nano-particle is 40-70nm.
Embodiment 7：Transparent self-cleaning coating containing Nano particles of silicon dioxide (MSiO2) 1
Nano particles of silicon dioxide (the MSiO for taking 2mL embodiments 1 to synthesize2) 1 alcohol dispersion liquid, diluted with 4mL ethanol, plus
Enter 0.4mL n-hexyl alcohols, 0.05mL butyl acrylates, 0.01g benzophenone is well mixed to form clear solution, obtain transparent from clear
Clean coating.Coating is coated on glass surface and is surface-treated, and after solvent volatilization solidifies 3 minutes, forms hyaline membrane.Film printing opacity
Rate 99.4%（As shown in Figure 1）, 153 ° of water contact angle（As shown in Figure 2）.
Embodiment 8：Contain Nano particles of silicon dioxide (ESiO2) 1 transparent self-cleaning coating
Take 2mL embodiments 2-in-1 into Nano particles of silicon dioxide (ESiO2) 1 alcohol dispersion liquid, diluted with 4mL ethanol, plus
Enter 0.4mL n-hexyl alcohols, 0.0.5mL GMAs, 0.01g salt compounded of iodine is well mixed to form clear solution, obtains
Transparent self-cleaning coating.Coating is coated on glass surface and is surface-treated, and after solvent volatilization solidifies 3 minutes, forms hyaline membrane.
Film light transmittance 99%, 151 ° of water contact angle.
Embodiment 9：Contain Nano particles of silicon dioxide (MSiO2) 2 transparent self-cleaning coating
Nano particles of silicon dioxide (the MSiO for taking 2mL embodiments 3 to synthesize2) 2 alcohol dispersion liquids, diluted with 5mL ethanol, plus
Enter 0.5mL n-butanols, 0.05mL butyl acrylates, 0.01g benzophenone is well mixed to form clear solution, obtain transparent from clear
Clean coating.Coating is coated on glass surface and is surface-treated, and after solvent volatilization solidifies 3 minutes, forms hyaline membrane.Film printing opacity
Rate 98%, 155 ° of water contact angle.
Embodiment 10：Contain Nano particles of silicon dioxide (ESiO2) 2 transparent self-cleaning coating
Nano particles of silicon dioxide (the ESiO for taking 2mL embodiments 4 to synthesize2) 2 alcohol dispersion liquids, diluted with 5mL ethanol, plus
Enter 0.5mL n-butanols, 0.05mL GMAs, 0.01g benzophenone is well mixed to form clear solution,
Obtain transparent self-cleaning coating.Coating is coated on glass surface and is surface-treated, and after solvent volatilization solidifies 3 minutes, is formed transparent
Film.Film light transmittance 99%, 154 ° of water contact angle.
Embodiment 11：Contain Nano particles of silicon dioxide (MSiO2) 3 transparent self-cleaning coating
Nano particles of silicon dioxide (the MSiO for taking 2mL embodiments 1 to synthesize2) 3 alcohol dispersion liquids, diluted with 4mL ethanol, plus
Enter 0.4mL n-hexyl alcohols, 0.06mL butyl acrylates, 0.01g benzophenone is well mixed to form clear solution, obtain transparent from clear
Clean coating.Coating is coated on glass surface and is surface-treated, and after solvent volatilization solidifies 3 minutes, forms hyaline membrane.Film printing opacity
Rate 98%, 152 ° of water contact angle.
Embodiment 12：Contain Nano particles of silicon dioxide (ESiO2) 3 transparent self-cleaning coating
Take 2mL embodiments 2-in-1 into Nano particles of silicon dioxide (ESiO2) 3 alcohol dispersion liquids, diluted with 4mL ethanol, plus
Enter 0.4mL n-hexyl alcohols, 0.06mL GMAs, 0.01g salt compounded of iodine is well mixed to form clear solution, obtains
Transparent self-cleaning coating.Coating is coated on glass surface and is surface-treated, and after solvent volatilization solidifies 3 minutes, forms hyaline membrane.
Film light transmittance 99%, 150 ° of water contact angle.
Claims (4)
1. a kind of transparent super-hydrophobic automatic cleaning coating, it is characterised in that the coating is with the hydrophobic silica of active group
The one-component curing system that nano-particle, alcohols solvent and auxiliary agent are mixed to form；
The Nano particles of silicon dioxide hydrophobic with active group is by tetraethyl orthosilicate, silane coupler, siliceous amine alkane warp
Cross direct hydrolysis synthesis；
The Nano particles of silicon dioxide content hydrophobic with active group is the 1%- of total coating system mixture weight
10%；
The alcohols solvent be by ethanol and isopropanol, n-butanol, n-hexyl alcohol, what one or both of n-octyl alcohol was mixed
Mixed solvent；The alcohols solvent content is the 90%-98% of total coating system mixture weight；
The auxiliary agent includes one kind and 2- in butyl acrylate, allyl methacrylate, GMA
One kind in hydroxy-2-methyl -1- phenylacetones, benzophenone, salt compounded of iodine is mixed；The auxiliary agent content is total coating
The 0.1%-1% of system mixture weight；
The silane coupler is the silane with active group, including one kind in KH570, KH560, KH561, siliceous amine alkane
Be can fast hydrolyzing produce ammonia catalysis tetraethyl orthosilicate generation Nano particles of silicon dioxide, while to nano-particle carry out it is hydrophobic
In a modified class compound, including HMDS, divinyl tetramethyl disilazane, tetramethyl disilazane
It is a kind of；
The active group is acrylate-based or epoxy radicals.
2. a kind of transparent super-hydrophobic automatic cleaning coating according to claim 1, it is characterised in that after the coating film forming thoroughly
Light rate is more than 98%, and water contact angle is more than 150 °, with good self-cleaning performance.
3. a kind of transparent super-hydrophobic automatic cleaning coating according to claim 1, it is characterised in that the nano particle diameter
For 10-200nm.
4. a kind of transparent super-hydrophobic automatic cleaning coating according to claim 1, it is characterised in that the preparation method of the coating
Using the Nano particles of silicon dioxide of a step direct hydrolysis method anamorphic zone active hydrophobic group, then coating is prepared, obtain high transparency
Self-cleaning coating.
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| CN105419442A (en) * | 2015-12-08 | 2016-03-23 | 佛山市雅洁源科技股份有限公司 | Self-cleaning material |
| CN105484018B (en) * | 2016-01-04 | 2017-08-01 | 东华大学 | A kind of preparation method of easy decontamination jacquard fabric |
| CN106497196A (en) * | 2016-10-07 | 2017-03-15 | 常州创索新材料科技有限公司 | A kind of preparation method of high intensity automatically cleaning automotive material |
| CN108299913B (en) * | 2016-10-08 | 2020-09-01 | 深圳宝顺美科技有限公司 | Hydrophobic coating material and hydrophobic coating |
| CN106752125A (en) * | 2016-11-22 | 2017-05-31 | 赖禄波 | Antisticking coating and preparation method |
| CN106833277A (en) * | 2017-02-23 | 2017-06-13 | 苏州适乐科技有限公司 | A kind of solar heat-collection plate coating material and its preparation technology |
| CN109096914B (en) * | 2018-07-16 | 2021-01-15 | 武汉疏能新材料有限公司 | Preparation method of super-hydrophobic coating and film with hydrophobic migration property |
| CN109096803A (en) * | 2018-07-16 | 2018-12-28 | 武汉疏能新材料有限公司 | Transparent hydrophobic SiO2The preparation method and application of nano functional liquid |
| CN110103826B (en) * | 2019-03-28 | 2021-12-14 | 上海赫千电子科技有限公司 | Image display equipment and method of electronic rearview mirror |
| CN110157319A (en) * | 2019-05-16 | 2019-08-23 | 苏州赛伍应用技术股份有限公司 | A kind of coating, coating, transparent back panel and preparation method |
| CN114752292A (en) * | 2022-04-24 | 2022-07-15 | 扬州工业职业技术学院 | High-molecular coating liquid for self-cleaning glass and preparation method thereof |
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| CN101544476A (en) * | 2008-03-28 | 2009-09-30 | 皮尔金顿集团有限公司 | Super-hydrophobic transparent coating and preparation method thereof |
| CN101824278A (en) * | 2010-04-06 | 2010-09-08 | 南京工业大学 | Superhydrophobic inorganic organic nano composite polymeric coating material and preparation method thereof |
| US9221076B2 (en) * | 2010-11-02 | 2015-12-29 | Ut-Battelle, Llc | Composition for forming an optically transparent, superhydrophobic coating |
| CN104449357B (en) * | 2014-11-26 | 2017-01-04 | 浙江大学 | A kind of transparent hydrophobic coating material and the method preparing transparent hydrophobic coating thereof |
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